Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

Lattice-Boltzmann simulations of the capillary pressure–saturation–interfacial area relationship for porous media

Hysteresis in the relationship between capillary pressure (P_c), wetting phase saturation (S_w) and nonwetting–wetting interfacial area per volume (a_nw) is investigated using multiphase lattice-Boltzmann simulations of drainage and imbibition in a glass bead porous system. In order to validate the simulations, the P_c–S_w and a_nw–S_w main hysteresis loops were compared to experimental data reported by Culligan et al. [Culligan KA, Wildenschild D, Christensen BS, Gray WG, Rivers ML, Tompson AB. Interfacial area measurements for unsaturated flow through porous media. Water Resour Res 2004;40:W12413]. In general, the comparison shows that the simulations are reliable and capture the important physical processes in the experimental system. P_c–S_w curves, a_nw–S_w curves and phase distributions (within the pores) show good agreement during drainage, but less satisfactory agreement during imbibition. Drainage and imbibition scanning curves were simulated in order to construct P_c–S_w–a_nw surfaces. The root mean squared error (RMSE) and mean absolute error (MAE) between drainage and imbibition surfaces was 0.10 mm⁻¹ and 0.03 mm⁻¹, respectively. This small difference indicates that hysteresis is virtually nonexistent in the P_c–S_w–a_nw relationship for the multiphase system studied here. Additionally, a surface was fit to the main loop (excluding scanning curves) of the drainage and imbibition P_c–S_w–a_nw data and compared to the surface fit to all of the data. The differences between these two surfaces were small (RMSE = 0.05 mm⁻¹ and MAE = 0.01 mm⁻¹) indicating that the P_c–S_w–a_nw surface is adequately represented without the need for the scanning curve data, which greatly reduces the amount of data required to construct the non-hysteretic P_c–S_w–a_nw surface for this data.     

Internal soil moisture and piezometric responses to rainfall-induced shallow slope failures

Better knowledge regarding internal soil moisture and piezometric responses in the process of rainfall-induced shallow slope failures is the key to an effective prediction of the landslide and/or debris flow initiation. To this end, internal soil moisture and piezometric response of 0.7-m-deep, 1.5-m-wide, 1.7-m-high, and 3.94-m-long semi-infinite sandy slopes rested on a bi-linear impermeable bedrock were explored using a chute test facility with artificial rainfall applications. The internal response time defined by the inflection point of the soil moisture and piezometric response curves obtained along the soil–bedrock interface were closely related to some critical failure states, such as the slope toe failure and extensive slope failures. It was also found that the response times obtained at the point of abrupt bedrock slope decrease can be used as indicators for the initiation of rainfall-induced shallow slope failures. An investigation of spatial distributions of soil water content, ω (or degrees of saturation, S_r), in the slope at critical failure states shows that the 0.2 m – below – surface zone remains unsaturated with S_r 40–60%, regardless of their distances from the toe and the rainfall intensity. Non-uniform distributions of ω (or S_r) along the soil–bedrock interface at critical failure states were always associated with near-saturation states (S_r 80–100%) around the point of bedrock slope change or around the transient ‘toe’ upstream of the slumped mass induced by the retrogressive failure of the slope. These observations suggest the important role of the interflow along the soil–bedrock interface and the high soil water content (or high porewater pressure) around the point of bedrock slope deflection in the rainfall-induced failure of sandy slopes consisting of shallow impermeable bedrocks. The present study proposes an ‘internal response time’ criterion to substantiate the prediction of rainfall-induced shallow slope failures. It is believed that the ‘internal response time’ reflects the overall characteristics of a slope under rainfall infiltration and can be as useful as the conventional meteorology-based threshold times. The ‘internal response time’ theory can be generalized via numerical modeling of slope hydrology, slope geology and slope stability in the future.     

Sensitivity of hydrological variables to climate change in the Haihe River basin,China

Using the defined sensitivity index, the sensitivity of streamflow, evapotranspiration and soil moisture to climate change was investigated in four catchments in the Haihe River basin. Climate change contained three parts: annual precipitation and temperature change and the change of the percentage of precipitation in the flood season (P_f). With satisfying monthly streamflow simulation using the variable infiltration capacity model, the sensitivity was estimated by the change of simulated hydrological variables with hypothetical climatic scenarios and observed climatic data. The results indicated that (i) the sensitivity of streamflow would increase as precipitation or P_f increased but would decrease as temperature increased; (ii) the sensitivity of evapotranspiration and soil moisture would decrease as precipitation or temperature increased, but it to P_f varied in different catchments; and (iii) hydrological variables were more sensitive to precipitation, followed by P_f, and then temperature. The nonlinear response of streamflow, evapotranspiration and soil moisture to climate change could provide a reference for water resources planning and management under future climate change scenarios in the Haihe River basin. Copyright © 2011 John Wiley & Sons, Ltd.     

The behaviour of metals and sulphur during the formation of hydrothermal mercury–antimony–arsenic mineralization, Uzon caldera, Kamchatka, Russia

Uzon caldera, located in the eastern volcanic belt of the Kamchatka peninsula, is a complicated structure of Middle Pleistocene age. The composition of the co-existing solid and fluid phases, temperature and pH were determined with the aim of establishing the distribution of sulphur species, As, Sb and the main ore-forming metals. In the solid samples, the following sulphur-bearing minerals were identified: pyrite, realgar, orpiment, alacranite (As₈S₉), uzonite (As₄S₅), amorphous As-sulphide, stibnite, cinnabar and native sulphur. The following sulphur-bearing species H₂S, H₂S₂+S₅²⁻(aq)(aqueous polysulphanes), S⁰(aq), SO₃²⁻(aq), S₂O₃²⁻, SO₄²⁻ and total concentration of sulphur were determined in solutions. Eh, pH and H₂S concentration were measured potentiometrically in situ. Zero-valent sulphur (S⁰(aq)+H₂S₂+S₅²⁻(aq)) predominates in Uzon solutions. The pair H₂S–S_colloidal is Eh-determining in Uzon solutions up to 75–85°C. A quantitative thermodynamic model of the mineral deposition process at Uzon was constructed using the collected data. It was obtained that the composition of the hydrothermal solution and the precipitation of Sb–As–Hg species can be described using two only main factors: the initial composition of fluid and the temperature variation.     

Determination of thermodynamic properties of (Fe,Mg)-pyroxenes at 1000 K by the emf method

Emf measurements were made on the cell Pt|Fe,(Fe,Mg)_xSi₂O₆,SiO₂|(ZrO₂)_0.85(CaO)_0.15|Fe,FeO|Pt at 1000 K. Using the present data, the standard free energy of formation of ferrosilite (compound FeSiO₃), from the component oxides FeO and SiO₂, is calculated to be −6.35 ± 0.80 kJ/mol. The activity-composition relation for pyroxene solid solution shows that it has a positive deviation from ideality at 1000 K. The present results are compared with the results of other workers.ΔG_mix andΔG^ex are calculated and plotted againstN_FeSiO3.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Self-diffusion studies of pore fluids in unconsolidated sediments by PFG NMR

The self-diffusion of water and hexadecane in medium and coarse sands from glacial sand deposits in central Germany were investigated by pulsed field gradient nuclear magnetic resonance (PFG NMR). Due to the restriction of the diffusion path at the pore/grain interface, the measured apparent self-diffusion coefficients (D(Δ)) in the pore space depend on the observation time (Δ) in the PFG NMR experiment. Although the bulk self-diffusion coefficients of water and hexadecane differ by about one order of magnitude, the apparent self-diffusion coefficients in the pore space obey the same characteristic time-behaviour, which depends only on geometrical properties of the pore system. Using the “short-time diffusion” model, surface-to-volume (S/V) ratios and inherent self-diffusion coefficients (D₀) of the pore fluids were extracted from these diffusion measurements. The S/V ratios obtained are independent of the pore fluid used and agree with known geometrical properties of the sand grains. Moreover, the D₀ values are consistent with the corresponding bulk self-diffusion coefficients measured separately. In contrast to these results of PFG NMR, simultaneous investigations of longitudinal (T₁) nuclear magnetic relaxation reveal that the relaxation time of the pore fluid is a less suitable parameter for a quantitative estimation of geometrical properties of the pore/grain interface in these unconsolidated sediments since it depends on chemical properties of the fluid/grain interface.     

A shot noise model for the generation of soil moisture data

An attempt is made to estimate the expected contribution of rainfall to soil moisture during the irrigation season. Effective rainfall and evapotranspiration are the parameters considered in the water balance carried out in the root zone. Rainfall occurrence is simulated by a Poisson process whereas evapotranspiration is described by a simple deterministic function of potential evapotranspiration and soil moisture in the root zone. Using the theory of shot noise models a closed form solution is derived from the expected soil moisture in the root zone at the end of the time interval (0,t]. For illustration purposes the proposed model is applied to a series of data from Mikra meteorological station in Greece.List of symbols x change in water storage in the root zone during the time interval t - X infiltrated rainfall of thei th storm event - ET actual evapotranspiration during thej th day - Poisson rate - number of storm events in (0,t] - t _r duration of rainfall - t _b interarrival time - h _i rainfall depth of thei th storm event - i _m mean rainfall intensity - i(t) instantaneous rainfall intensity - x(0),x(t) available soil moisture in the root zone at time 0 andt, respectively - PET potential evapotranspiration rate - x _F available soil moisture in the root zone at field capacity - soil moisture depletion rate (=PET/x _F ) - w impulse shape of filtered Poisson processes - E[·] mean value - S _i time of thei th rainfall event - N(t) time of storm events in (0,t] - estimated standard deviation The following symbols were used in this paper     

Fine S wave velocity structure beneath Iwate volcano, northeastern Japan, as derived from receiver functions and travel times

A genetic algorithm inversion of receiver functions derived from a dense seismic network around Iwate volcano, northeastern Japan, provides the fine S wave velocity structure of the crust and uppermost mantle. Since receiver functions are insensitive to an absolute velocity, travel times of P and S waves propagating vertically from earthquakes in the subducting slab beneath the volcano are involved in the inversion. The distribution of velocity perturbations in relation to the hypocenters of the low-frequency (LF) earthquakes helps our understanding of deep magmatism beneath Iwate volcano. A high-velocity region (dV_S/V_S=10%) exists around the volcano at depths of 2–15 km, with the bottom depth decreasing to 11 km beneath the volcano’s summit. Just beneath the thinning high-velocity region, a low-velocity region (dV_S/V_S=−10%) exists at depths of 11–20 km. Intermediate-depth LF (ILF) events are distributed vertically in the high-velocity region down to the top of the low-velocity region. This distribution suggests that a magma reservoir situated in the low-velocity region supplies magma to a narrow conduit that is detectable by the hypocenters of LF earthquakes. Another broad low-velocity region (dV_S/V_S=−5 to −10%) occurs at depths of 17–35 km. Additional clusters of deep LF (DLF) events exist at depths of 32–37 km in the broad low-velocity zone. The DLF and ILF events are the manifestations of magma movement near the Moho discontinuity and in the conduit just beneath the volcano, respectively.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

Numerical simulations of transport of non-ergodic solute plumes in heterogeneous aquifers

Transport of non-ergodic solute plumes by steady-state groundwater flow with a uniform mean velocity, μ, were simulated with Monte Carlo approach in a two-dimensional heterogeneous and statistically isotropic aquifer whose transmissivity, T, is log-normally distributed with an exponential covariance. The ensemble averages of the second spatial moments of the plume about its center of mass, <S _{i i} (t)>, and the plume centroid covariance, R _{i i} (t) (i=1,2), were simulated for the variance of Y=log T, σ _Y ²=0.1, 0.5 and 1.0 and line sources normal or parallel to μ of three dimensionless lengths, 1, 5, and 10. For σ _Y ²=0.1, all simulated <S _{i i} (t)>−S _{i i} (0) and R _{i i} (t) agree well with the first-order theoretical values, where S _{i i} (0) are the initial values of S _{i i} (t). For σ _Y ²=0.5 and 1.0 and the line sources normal to μ, the simulated longitudinal moments, <S ₁₁(t)>−S ₁₁(0) and R ₁₁(t), agree well with the first-order theoretical results but the simulated transverse moments <S ₂₂(t)>−S ₂₂(0) and R ₂₂(t) are significantly larger than the first-order values. For the same two larger values of σ _Y ² but the line sources parallel to μ, the simulated <S ₁₁(t)>−S ₁₁(0) are larger than but the simulated R ₁₁ are smaller than the first-order values, and both simulated <S ₂₂(t)>−S ₂₂(0) and R ₂₂(t) stay larger than the first-order values. For a fixed value of σ _Y ², the summations of <S _{i i} (t)>−S _{i i} (0) and R _{i i} , i.e., X _{i i} (i=1,2), remain almost the same no matter what kind of source simulated. The simulated X ₁₁ are in good agreement with the first-order theory but the simulated X ₂₂ are significantly larger than the first-order values. The simulated X ₂₂, however, are in excellent agreement with a previous modeling result and both of them are very close to the values derived using Corrsin's conjecture. It is found that the transverse moments may be significantly underestimated if less accurate hydraulic head solutions are used and that the decreasing of <S ₂₂(t)>−S ₂₂(0) with time or a negative effective dispersivity, defined as , may happen in the case of a line source parallel to μ where σ _Y ² is small.     

A quadratic element method for evaluating groundwater flow by the inversion of surface tilt with application to the Tono Area, Japan

By modifying a previous method with constant elements, we developed a quadratic element method for more accurately estimating groundwater flow by the inversion of tilt data. In this method: (1) a region of groundwater flow is divided into quadratic elements in which the change in groundwater volume per unit volume of rock (Δv) and the Skempton coefficient (B) vary in a quadratic manner with the coordinates, (2) the values of Δv are set to zero at the boundaries of the region of groundwater flow and (3) the sum of the squared second derivatives of Δv is adopted as a constraining condition that is weighted and added to the sum of the squared errors in tilt. First, analyses were performed for a flow model to determine the accuracy of this method for estimating groundwater flow and also to clarify the effect of the assumed size of a region of groundwater flow. These analyses showed that the quadratic element method proposed in this study gives a much better estimation of Δv than the constant element method and that a large region of groundwater flow should be assumed, rather than a small region, since the values of Δv at points outside of the actual region of groundwater flow are estimated to be nearly zero when a large region is assumed while these values are greatly overestimated when an excessively small region is assumed. Finally, the quadratic element method was applied to the site of the Mizunami Underground Research Laboratory in the Tono area, Japan. Inverse analyses were performed for tilt data measured by four tiltmeters with a resolution of 10⁻⁹ radians during the excavation of two shafts under the assumption that the rock mass is an isotropic and homogeneous half- space. The results showed that the method proposed in this study reproduced the tilt data very accurately. Thus, the distribution of Δv was estimated without sacrificing the reproducibility of the tilt data. The contour maps of B(1 + ν)Δv (ν: Poisson’s ratio) showed that the heterogeneous flow of groundwater occurred at the site and that groundwater volume decreased mainly in the area surrounded by two faults. The latter result is consistent with the finding obtained by previous investigations that these faults have low permeability in the direction perpendicular to the strike and may act as a flow barrier.     

Numerical simulations of transport of non-ergodic solute plumes in heterogeneous aquifers

Transport of non-ergodic solute plumes by steady-state groundwater flow with a uniform mean velocity, μ, were simulated with Monte Carlo approach in a two-dimensional heterogeneous and statistically isotropic aquifer whose transmissivity, T, is log-normally distributed with an exponential covariance. The ensemble averages of the second spatial moments of the plume about its center of mass, <S _{i i} (t)>, and the plume centroid covariance, R _{i i} (t) (i=1,2), were simulated for the variance of Y=log T, σ _Y ²=0.1, 0.5 and 1.0 and line sources normal or parallel to μ of three dimensionless lengths, 1, 5, and 10. For σ _Y ²=0.1, all simulated <S _{i i} (t)>−S _{i i} (0) and R _{i i} (t) agree well with the first-order theoretical values, where S _{i i} (0) are the initial values of S _{i i} (t). For σ _Y ²=0.5 and 1.0 and the line sources normal to μ, the simulated longitudinal moments, <S ₁₁(t)>−S ₁₁(0) and R ₁₁(t), agree well with the first-order theoretical results but the simulated transverse moments <S ₂₂(t)>−S ₂₂(0) and R ₂₂(t) are significantly larger than the first-order values. For the same two larger values of σ _Y ² but the line sources parallel to μ, the simulated <S ₁₁(t)>−S ₁₁(0) are larger than but the simulated R ₁₁ are smaller than the first-order values, and both simulated <S ₂₂(t)>−S ₂₂(0) and R ₂₂(t) stay larger than the first-order values. For a fixed value of σ _Y ², the summations of <S _{i i} (t)>−S _{i i} (0) and R _{i i} , i.e., X _{i i} (i=1,2), remain almost the same no matter what kind of source simulated. The simulated X ₁₁ are in good agreement with the first-order theory but the simulated X ₂₂ are significantly larger than the first-order values. The simulated X ₂₂, however, are in excellent agreement with a previous modeling result and both of them are very close to the values derived using Corrsin's conjecture. It is found that the transverse moments may be significantly underestimated if less accurate hydraulic head solutions are used and that the decreasing of <S ₂₂(t)>−S ₂₂(0) with time or a negative effective dispersivity, defined as , may happen in the case of a line source parallel to μ where σ _Y ² is small.     

Effective barometric admittance and gravity residuals

In the analysis of surface gravity signals that may originate from the Earth's core, the step of correcting for the atmospheric pressure fluctuations is one that must be done carefully. We apply two techniques for determining the local, or effective, barometric admittance function between simultaneous observations of surface gravity and pressure. The first is a frequency domain fit that computes the admittance on a band-by-band basis. Using data from both the Canadian and French superconducting gravimeters we determined that the magnitude of the local, or background, admittance increases smoothly and monotonically from about 0.2 μgal mbar⁻¹ at long periods (> 10 days) to about 0.35 μgal mbar⁻¹ at frequencies greater than 3 cycles per day (c.p.d.); the phase lag is within a few degrees of 180°. By comparison, the effective admittances of the large-scale harmonics of the solar heating tide (S₁---S₇) are much smaller, between 0.1 and 0.3 μgal mbar⁻¹, for most of the harmonics of a day. In the second approach we fit a symmetrical time domain admittance function having lengths between 1 and 19 h using both a standard least-squares fit to a white noise residual and a new, and clearly superior, fit assuming a brown noise residual. Both time and frequency domain approaches give comparable results and contribute to a significant lowering of the residual level in non-tidal bands.     

Temperature dependence of the oxygen isotopic fractionation between diatom silica and water

We present a new paleotemperature scale, based on the oxygen isotopic ratio of the non-exchangeable fraction of the oxygen from diatom silica. The equation t = 17.2 − 2.4 (δ¹⁸O_silica − δ¹⁸O_water − 40) − 0.2 (δ¹⁸O_silica − δ¹⁸O_water − 40)² was derived using recent sediment samples from different oceanic areas, the temperature and isotopic composition of the local surface water. Comparison of our results with other relationships established for quartz-water or amorphous silica-water at higher temperature suggests no difference in isotopic fractionation between quartz-water and biogenic silica-water couples.     

Energy mode distribution: An analysis of the ratio of anti-Stokes to Stokes amplitudes generated by a pair of counterpropagating Langmuir waves

Results from plasma wave experiments in spacecrafts give support to nonlinear interactions involving Langmuir, electromagnetic, and ion-acoustic waves in association with type III solar radio bursts. Starting from a general form of Zakharov equation (Zakharov, V.E., 1985. Collapse and self-focusing of Langmuir waves. Hand-book of Plasma Physics Cap.2, 81–121) the equations for electric fields and density fluctuations (density gratings) induced by a pair of counterpropagating Langmuir waves are obtained. We consider the coupling of four triplets. Each two triplets have in common the Langmuir pump wave (forward or backward wave) and a pair of independent density gratings. We numerically solve the dispersion relation for the system, extending the work of (Alves, M.V., Chian, A.C.L., Moraes, M.A.E., Abalde, J.R., Rizzato, F.B., 2002. A theory of the fundamental plasma emission of type- III solar radio bursts. Astronomy and Astrophysics 390, 351–357). The ratio of anti-Stokes (AS) (ω₀+ω) to Stokes (S) (ω₀-ω^*) electromagnetic mode amplitudes is obtained as a function of the pump wave frequency, wave number, and energy. We notice that the simultaneous excitation of AS and S distinguishable modes, i.e., with Re{ω}=ω_r≠0, only occurs when the ratio between the pump wave amplitudes, r is ≠1 and the pump wave vector k₀ is , W₀ being the forward pump wave energy. We also observe that the S mode always receives more energy.     

High-resolution garnet chronometry and the rates of metamorphic processes

Garnets in an amphibolite-facies metasediment from Sulitjelma, North Norway yield precise and concordant SmNd, UPb and RbSr ages that relate directly to the pressure (P) and temperature (T) conditions of mineral growth. Differential mineral reaction between graphitic and non-graphitic layers within this sample preserves a record of theP-T and time (t) history experienced during Barrovian regional metamorphism. Garnets in graphitic layers grew during prograde metamorphism at462 ± 16°C and5.2 ± 0.5 kbar under conditions of lowaH₂O, and yield indistinguishable¹⁴⁷Sm¹⁴³Nd and²³⁸U²⁰⁶Pb ages of434.1 ± 1.2 Ma and433.9 ± 1.0 Ma, respectively. In contrast, garnet growth in adjacent graphite-free layers did not occur untilP-T conditions of540 ± 18°C and8.0 ± 1.0 kbar were attained, with continued growth in response to minor heating and decompression with final matrix equilibration at544 ± 16°C and7.0 ± 1.0 kbar. The inclusion-free garnet rims in this assemblage record indistinguishable¹⁴⁷Sm¹⁴³Nd and²³⁸U²⁰⁶Pb ages of424.6 ± 1.2 Ma and423.4± 1.7 Ma, respectively. These results provide precise estimates for average heating and burial rates during prograde metamorphism of 8.6_−4.4^+7.5°C Ma⁻¹ and 0.8_−0.5^+0.9 km Ma⁻¹, respectively. Rb and Sr exchange between coexisting silicates in the graphite-free assemblage continued for some 37 Ma after the “peak” of metamorphism, and require an average cooling rate of about 4.0°C Ma⁻¹ during uplift. These results illustrate a clear relationship between reaction history and the timing of mineral growth and provide definitive constraints on the rates of thermal and tectonic processes accompanying regional metamorphism.     

Respiratory adaptations to oxygen lack in three species of Glossiphoniidae (Hirudinea) in Lake Esrom, Denmark

The weight-specific respiration rate (μl O₂ mg⁻¹ AFDW h⁻¹) of three species of leech from Lake Esrom, Denmark, Glossiphonia concolor, G. complanata and Helobdella stagnalis was measured in a closed stirred chamber with a micro electrode. At declining oxygen concentration (mg O₂ l⁻¹) all three species expressed moderate ability to regulate respiration, in G. concolor and G. complanata down to 2 mg O₂ l⁻¹, in H. stagnalis down to 0.75 mg O₂ l⁻¹. Survival in anoxia was measured in closed bottles. The time to 50% survival (LD₅₀) was 30 days in G. concolor at 20 °C and 30 and 4 days in H. stagnalis at 10 and 20 °C, respectively. The results were discussed in relation to habitat and spatial distribution of the three species in the lake.     

Thermal equation of state of magnesite to 32 GPa and 2073 K

Pressure–volume–temperature relations have been measured to 32 GPa and 2073 K for natural magnesite (Mg_0.975Fe_0.015Mn_0.006Ca_0.004CO₃) using synchrotron X-ray diffraction with a multianvil apparatus at the SPring-8 facility. A least-squares fit of the room-temperature compression data to a third-order Birch–Murnaghan equation of state (EOS) yielded K₀ = 97.1 ± 0.5 GPa and K′ = 5.44 ± 0.07, with fixed V₀ = 279.55 ± 0.02 Å³. Further analysis of the high-temperature compression data yielded the temperature derivative of the bulk modulus (∂K_T/∂T)_P = −0.013 ± 0.001 GPa/K and zero-pressure thermal expansion α = a₀ + a₁T with a₀ = 4.03 (7) × 10⁻⁵ K⁻¹ and a₁ = 0.49 (10) × 10⁻⁸ K⁻². The Anderson–Grüneisen parameter is estimated to be δ_T = 3.3. The analysis of axial compressibility and thermal expansivity indicates that the c-axis is over three times more compressible (K_Tc = 47 ± 1 GPa) than the a-axis (K_Tc = 157 ± 1 GPa), whereas the thermal expansion of the c-axis (a₀ = 6.8 (2) × 10⁻⁵ K⁻¹ and a₁ = 2.2 (4) × 10⁻⁸ K⁻²) is greater than that of the a-axis (a₀ = 2.7 (4) × 10⁻⁵ K⁻¹ and a₁ = −0.2 (2) × 10⁻⁸ K⁻²). The present thermal EOS enables us to accurately calculate the density of magnesite to the deep mantle conditions. Decarbonation of a subducting oceanic crust containing 2 wt.% magnesite would result in a 0.6% density reduction at 30 GPa and 1273 K. Using the new EOS parameters we performed thermodynamic calculations for magnesite decarbonation reactions at pressures to 20 GPa. We also estimated stability of magnesite-bearing assemblages in the lower mantle.